(10R,11R,12S,13R)-3,11,13-trimethyl-8-oxa-1-azatetracyclo[10.2.1.02,7.010,13]pentadeca-2,4,6-triene-14,15-dione | 1613169-90-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: (10R,11R,12S,13R)-3,11,13-trimethyl-8-oxa-1-azatetracyclo[10.2.1.02,7.010,13]pentadeca-2,4,6-triene-14,15-dione
• CAS: 1613169-90-6
• 化学式: C₁₆H₁₇NO₃
• 分子量: 271.316
• InChiKey: SHTOCYKJGRLQBY-NKTGWMFESA-N

物化性质

• 沸点：
  469.3±45.0 °C(predicted)
• 密度：
  1.31±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-氨基-3-甲基苯酚 在 9-噻吨酮 、 potassium carbonate 作用下， 以 丙酮 、 甲苯 、 乙腈 为溶剂， 反应 6.0h， 生成 (10R,11R,12S,13R)-3,11,13-trimethyl-8-oxa-1-azatetracyclo[10.2.1.02,7.010,13]pentadeca-2,4,6-triene-14,15-dione
  参考文献：
  名称：

  Tailoring Atropisomeric Maleimides for Stereospecific [2 + 2] Photocycloaddition—Photochemical and Photophysical Investigations Leading to Visible-Light Photocatalysis

  摘要：

  Atropisomeric maleimides were synthesized and employed for stereospecific [2 + 2] photocycloaddition. Efficient reaction was observed under direct irradiation, triplet-sensitized UV irradiation, and non-metal catalyzed visible-light irradiation, leading to two regioisomeric (exo/endo) photoproducts with complete chemoselectivity (exclusive [2 + 2] photoproduct). High enantioselectivity (ee > 98%) and diastereoselectivity (dr > 99:1%) were observed under the employed reaction conditions and were largely dependent on the substituent on the maleimide double bond but minimally affected by the substituents on the alkenyl tether. On the basis of detailed photophysical studies, the triplet energies of the maleimides were estimated. The triplet lifetimes appeared to be relatively short at room temperature as a result of fast [2 + 2] photocycloaddition. For the visible-light mediated reaction, triplet energy transfer occurred with a rate constant close to the diffusion-limited value. The mechanism was established by generation of singlet oxygen from the excited maleimides. The high selectivity in the photoproduct upon reaction from the triplet excited state was rationalized on the basis of conformational factors as well as the type of diradical intermediate that was preferred during the photoreaction.

  DOI：

  10.1021/ja5034638